CN102874801A - Preparation method for graphene - Google Patents
Preparation method for graphene Download PDFInfo
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- CN102874801A CN102874801A CN2012103908828A CN201210390882A CN102874801A CN 102874801 A CN102874801 A CN 102874801A CN 2012103908828 A CN2012103908828 A CN 2012103908828A CN 201210390882 A CN201210390882 A CN 201210390882A CN 102874801 A CN102874801 A CN 102874801A
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Abstract
The invention provides a preparation method for graphene. The method comprises the following steps of: heating a semiconductor substrate under the atmosphere of hydrogen and the inert atmosphere to 810 to 910 DEG C; keeping the temperature unchanged, and introducing a carbon source; reacting on the surface of the semiconductor substrate by a chemical vapor deposition method; and after reaction, closing the carbon source, and cooling under the atmosphere of hydrogen and the inert atmosphere to the room temperature to prepare the graphene on the surface of the semiconductor substrate. Compared with a method for growing the graphene on the surface of the conventional substrate by the chemical vapor deposition method, the method for directly synthesizing the graphene on the surface of the semiconductor material has the advantage that the preparation process for the graphene is simplified; meanwhile, by adjusting reaction parameters, a large-size, zero-defect and high-quality graphene film of which the layer number can be controlled can be prepared; and moreover, the preparation method is compatible with the semiconductor industry, and the wide application of the graphene to the semiconductor industry can be promoted quickly.
Description
Technical field
The invention belongs to semiconductor applications, relate to a kind of preparation method of Graphene, particularly a kind of method that adopts preparing graphene through chemical vapor deposition.
Background technology
Graphene, namely the monoatomic layer of graphite is that carbon atom is according to sp
2The two-dirnentional structure with honeycomb arrangement that becomes key to form.The method that two scientists of Univ Manchester UK in 2004 use micromechanics to peel off has been found Graphene, and has obtained Nobel Prize in physics in 2010.
After Graphene is found, because it all has excellent performance at machinery, electricity, optics and chemistry, such as show long-range ballistic transport character under very high electronic mobility, the room temperature, band gap can be regulated and control etc., make it have huge application prospect, thereby academia, industry member get most of the attention to it, have caused the research boom in the fields such as physics and Materials science.The conductivity that Graphene is good and light transmission make it that extraordinary application prospect arranged aspect the transparent electrical conducting electrode, are expected to be widely used in the fields such as touch-screen based on Graphene, liquid-crystal display, organic photovoltaic battery, Organic Light Emitting Diode.The two-dirnentional structure of Graphene uniqueness makes it have bright application prospect in sensor field, for example, based on the gas detector on the basis of the controlled graphene film of big area, the number of plies, its huge surface-area makes it very responsive to environment on every side, even a gas molecule adsorbs or discharges can detect.
But the grapheme material problem that controlledly synthesis has specific morphology still is not resolved.Based on this, the research of Graphene still rests on the fundamental research field, and large-scale application of distance still has a segment distance.
At present the preparation method of Graphene mainly contain that micromechanics is peeled off, SiC subliming method, graphite oxide reduction method and chemical vapor deposition.The micromechanics stripping method can prepare high-quality Graphene, but the Graphene area of at present this method preparation can only be used for Basic Experiment Study less than 1 mm * 1 mm.The Graphene of SiC subliming method preparation is subjected to the impact of substrate very large, and number of plies heterogeneity can't be carried out substrate-transfer.The graphite oxide reduction method can a large amount of Graphene sample of chemical preparation, satisfies to a certain extent the industrial application requirement, yet because the introducing of oxygenant, has destroyed the conjugated structure of Graphene.Although chemical reduction and high-temperature heat treatment can be recovered the conjugated structure of Graphene to a certain extent, yet the intrinsic electric property of Graphene reduces greatly.
Chemical gaseous phase depositing process is the important method for preparing at present high quality big area Graphene, mainly due to its have low labour intensity, low cost, the characteristics such as be produced on a large scale.Recently, it is found that graphene film can be grown on the metallic films such as iron, cobalt, nickel, copper, and be easy to substrate-transfer, opened up the application prospect of high-quality graphene at microelectronic.Although growth mechanism is different, metal is considered to the catalyzer that is absolutely necessary in the process of growth of Graphene.
Because the existence of metal, Graphene can not directly be used to the assembling of graphene device.By means of polymkeric substance polymethacrylate (PMMA) for example, polydimethylsiloxane (PDMS) etc. utilize metal etch agent etching metal catalyst as medium transfer, have realized that Graphene is from metallic film to quartz substrate (SiO at present
2) and the silicon wafer-based with silica dioxide coating at the bottom of (S iO
2/ transfer on Si), thus further realized the assembling of high performance transparent graphene conductive film and FET device.Yet loaded down with trivial details transfer process is easy to cause the introducing of polymeric impurities and metallic impurity, weak adhesive attraction between the formation of fold and Graphene and the transfer substrate.Although realized the direct-assembling of Graphene in the silicon-dioxide substrate by means of thinner metal catalyst, simplified preparation technology, yet above-mentioned transfer shortcoming is difficult to still be overcome fully.Simultaneously, the controllability of this kind graphene film thickness is relatively poor, can grow multilayer film in uneven thickness on the nickel metal, and can only grow single thin film and a small amount of bilayer film on the copper.
Therefore how realizing that the controlled Graphene of the number of plies directly synthesizes in non-metallic material becomes study hotspot in the Graphene field.Patent CN 102161482 A disclose and have a kind ofly adopted the method for chemical vapor deposition growth Graphene at quartzy, silicon or with the silicon base of silica dioxide coating, and it has simplified the preparation technology of Graphene on metal base, and is simultaneously compatible with semi-conductor industry.But, do not relate on the one hand other non-metallic material except siliceous composition in this patent as the situation of base material (being catalytic substrate), for example, do not disclose Germanium semiconductor material as the situation of the base material of growing graphene, on the other hand, still have the D-band(D peak in the Raman of the Graphene for preparing in this patent (Raman) spectrum), namely still there is mass defect.
Summary of the invention
The shortcoming of prior art in view of the above the object of the present invention is to provide a kind of preparation method of Graphene, is used for solving prior art and can't be directly prepares the problem of the controlled and flawless high-quality graphene of the number of plies at semiconductor material.
Reach for achieving the above object other relevant purposes, the invention provides a kind of preparation method of Graphene, described preparation method comprises at least:
1) provides the semiconductor substrate;
2) under hydrogen and inert atmosphere, described semiconductor base is heated to 810 ~ 910 ℃;
3) keep step 2) in temperature-resistant, under hydrogen and inert atmosphere to step 2) reaction system in pass into carbon source, adopt the method for chemical vapour deposition in described step 2) the semiconductor-based basal surface that is disposed reacts;
4) reaction is closed described carbon source after complete, and is cooled to room temperature under hydrogen and inert atmosphere, finishes at described semiconductor-based basal surface to prepare Graphene.
Alternatively, described semiconductor base comprises germanium or gallium arsenide.
Alternatively, described carbon source is selected from least a of gaseous carbon source, liquid carbon source and solid-state carbon source.
Alternatively, described gaseous carbon source is methane, acetylene or ethene, and described liquid carbon source is methyl alcohol or ethanol, and described solid-state carbon source is polymethylmethacrylate, polystyrene, polydimethylsiloxane.
Alternatively, in the described step 3), the flow of described carbon source is 0.1 ~ 20sccm; The flow of described hydrogen is 2 ~ 100sccm; The described reaction times is 20 ~ 120min.
Alternatively, described step 1) also comprises the described semiconductor base step that cleans up of water, deionized water, ethanol and acetone respectively.
Alternatively, the Graphene for preparing in the described step 4) is individual layer or double-layer graphite alkene film.
As mentioned above, the preparation method of a kind of Graphene of the present invention, has following beneficial effect: compared to adopting chemical vapour deposition at conventional base (copper, nickel or quartz, silicon or with the silicon of silica dioxide coating etc.) surface growth Graphene, the present invention adopts chemical gaseous phase depositing process directly to prepare Graphene on semiconductor base, has simplified Graphene preparation technology; Simultaneously by adjusting reaction parameter (concentration ratio of rare gas element, carbonaceous material and hydrogen, temperature of reaction, reaction times), can prepare large size, the controlled Graphene of the number of plies, and there is not the D peak that represents defective in the Raman spectrum of the Graphene of the method preparation, namely eliminate Graphene mass defect, prepared the high-quality Graphene of zero defect; In addition, the present invention is compatible mutually with semi-conductor industry, can promote quickly Graphene in the widespread use in semi-conductor industry circle (fields such as high-performance transparent conductive film, solar cell, touch-screen and high-performance semiconductor device).
Description of drawings
Fig. 1 is shown as the Raman spectrum of the Graphene that the preparation method of a kind of Graphene of the present invention prepares in embodiment one.
Fig. 2 a is shown as the SiO that Graphene that the preparation method of a kind of Graphene of the present invention prepares is transferred to 300nm in embodiment one
2After optical microscope photograph.
Fig. 2 b is shown as scanning electron microscope (SEM) photo of the Graphene that the preparation method of a kind of Graphene of the present invention prepares in embodiment one.
Fig. 3 is shown as the Raman spectrum comparison diagram of the Graphene that the preparation method of a kind of Graphene of the present invention prepares under the different carbon source flow conditions in embodiment two.
Fig. 4 is shown as the Raman spectrum comparison diagram of the Graphene that the preparation method of a kind of Graphene of the present invention prepares under the condition of different temperatures in embodiment three.
Fig. 5 is shown as the Raman spectrum comparison diagram of the Graphene that the preparation method of a kind of Graphene of the present invention prepares under the differential responses time conditions in embodiment four.
Embodiment
Below by specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be used by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change under the spirit of the present invention not deviating from.
See also Fig. 1 to Fig. 5.Need to prove, the diagram that provides in the following embodiment only illustrates basic conception of the present invention in a schematic way, satisfy only show in graphic with the present invention in relevant assembly but not component count, shape and size drafting when implementing according to reality, kenel, quantity and the ratio of each assembly can be a kind of random change during its actual enforcement, and its assembly layout kenel also may be more complicated.
Chemical gaseous phase depositing process is the important method for preparing at present high quality big area Graphene, when utilizing chemical vapour deposition to realize that Graphene prepares in the prior art, a kind of is to adopt metallic substance (for example copper, nickel) as the catalyzer in the process of growth of Graphene, and another kind is that Graphene directly synthesizes in quartz, silicon or the substrates such as silicon with silica dioxide coating.Front a kind of method is owing to the existence of metal, and Graphene can not directly be used to the assembling of graphene device; Rear a kind of method, although simplified the preparation technology of Graphene on metal base, simultaneously compatible with semi-conductor industry, but, it does not relate to other non-metallic material except siliceous composition as the situation of base material (being catalytic substrate), for example, does not disclose Germanium semiconductor material as the situation of the base material of growing graphene, and still have the D-band(D peak in the Raman spectrum of the Graphene of its preparation), namely still there is mass defect.
In view of this, the invention provides a kind of preparation method of Graphene, compared to adopting chemical vapour deposition at conventional base (copper, nickel or quartz, silicon or with the silicon of silica dioxide coating etc.) surface growth Graphene, the present invention adopts chemical gaseous phase depositing process directly to prepare Graphene on semiconductor base, has simplified Graphene preparation technology; Simultaneously by adjusting reaction parameter (concentration ratio of rare gas element, carbonaceous material and hydrogen, temperature of reaction, reaction times), can prepare large size, the controlled Graphene of the number of plies, and there is not the D peak that represents defective in the Raman spectrum of the Graphene of the method preparation, namely eliminate Graphene mass defect, prepared the high-quality Graphene of zero defect; In addition, the present invention is compatible mutually with semi-conductor industry, can promote quickly Graphene in the widespread use in semi-conductor industry circle (fields such as high-performance transparent conductive film, solar cell, touch-screen and high-performance semiconductor device).Below will elaborate preparation method and the embodiment of a kind of Graphene of the present invention, and make those skilled in the art not need creative work can understand the preparation method of a kind of Graphene of the present invention.
Embodiment one
The invention provides a kind of preparation method of Graphene, described method comprises at least:
At first performing step 1) provide the semiconductor substrate as catalyzer, preferred, described semiconductor base according to sequencing respectively water, deionized water, ethanol and acetone clean up, wherein, described semiconductor base comprises germanium or gallium arsenide.In present embodiment one, because described semiconductor base is the germanium material substrate of exempting to clean, then do not need described cleaning step.Follow performing step 2).
In step 2) in, under hydrogen and inert atmosphere, described semiconductor base being heated to 810 ~ 910 ℃ in tube furnace, the flow of described hydrogen is 2 ~ 50sccm, preferably, the flow of described hydrogen is 30 ~ 50sccm.Particularly, in the present embodiment one, described hydrogen and inert atmosphere are selected hydrogen and argon gas (Ar), and wherein, hydrogen flowing quantity is 50sccm, and argon flow amount is 200sccm, and described semiconductor base is heated to 910 ℃ in tube furnace.Follow performing step 3).
In step 3), keep step 2) in temperature-resistant, under hydrogen and inert atmosphere, to step 2) reaction system in pass into carbon source, adopt the method for chemical vapour deposition in described step 2) the semiconductor-based basal surface that is disposed reacts.Wherein, described carbon source is selected from least a of gaseous carbon source, liquid carbon source and solid-state carbon source, described gaseous carbon source is methane, acetylene or ethene, described liquid carbon source is methyl alcohol or ethanol, and described solid-state carbon source is polymethacrylate (PMMA), polystyrene, polydimethylsiloxane (PDMS); The flow of described carbon source is 0.1 ~ 20sccm, and preferably, the flow of described carbon source is 0.1 ~ 5sccm; The flow of described hydrogen is 2 ~ 100sccm, and preferably, the flow of described hydrogen is 2 ~ 50sccm, 30 ~ 50sccm or 60 ~ 100sccm; The described reaction times is 20 ~ 120min, and preferably, the described reaction times is 60 ~ 100min.
Particularly, in present embodiment one, in step 3), keep step 2) in 910 ℃ temperature-resistant, namely temperature of reaction is 910 ℃, described inert atmosphere is selected argon gas (Ar), and its flow is 200sccm; Described hydrogen flowing quantity is 50sccm; Reaction times is 100min; Described carbon source is methane, but because device-restrictive, when the flow of input methane when being 0.1sccm, the argon gas that is input as 2sccm (Ar) of carbon source and the mixed gas of methane in the actual process, wherein argon gas (Ar) accounts for 95%, methane accounts for 5%, in other words, argon gas is 1.9sccm in the mixed gas of the argon gas of described 2sccm (Ar) and methane, and methane is 0.1sccm, at this moment, after adding the mixed gas carbon source of this argon gas (Ar) and methane, the actual flow of argon gas is 201.9sccm.Follow performing step 4).
In step 4), react and close described carbon source after complete, the stopped heating tube furnace, under hydrogen and inert atmosphere with step 3) in through the reaction semiconductor base be cooled to room temperature, finish at described semiconductor-based basal surface and prepare Graphene, wherein, according to the setting of differential responses parameter, the Graphene for preparing in the step 4) is individual layer or double-layer graphite alkene film.Particularly, the Graphene for preparing in present embodiment one is double-layer graphite alkene film.
Fig. 2 a is shown as the optical microscope photograph of the Graphene of preparation in the present embodiment one, and wherein, for the needs of optical imagery, described Graphene is transferred to the SiO of 300nm
2On, be film by the Graphene that can find out present embodiment one preparation among Fig. 2 a; Fig. 2 b is shown as scanning electron microscope (SEM) photo of the Graphene of preparation in the present embodiment one.
What need to further specify is that Raman spectrum is the advantageous methods that characterizes the Graphene number of plies and quality.Particularly, after the Graphene of present embodiment one (it is that 50sccm, carbon source methane are that 0.1sccm, argon gas (Ar) flow are that 201.9sccm, reaction times are 100min that the germanium substrate is heated to 910 ℃, hydrogen flowing quantity) preparation carried out the measurement of continuous 20 different sample spot, the Raman of tested each point (Raman) spectrum all as shown in Figure 1.In Fig. 1, the 2D peak position that the Graphene of preparation possesses halfwidth ~ 39cm-1 among the embodiment one is near 2700cm-1, and this 2D peak meets the match at single Lorentz peak, and because the relative intensity ratio I at G peak and 2D peak
G: I
2D≈ 1.2, belongs between 0.7 to 1.3 scope, and be double-layer graphite alkene according to the Graphene for preparing in the provable present embodiment one of this raman spectral characteristics; In Fig. 1, there is not simultaneously the D peak (D-band) that represents defective, then the Graphene of preparation is flawless high-quality graphene in the provable present embodiment one of this raman spectral characteristics, therefore, the Graphene of aforementioned each step preparation is flawless high quality double-layer graphite alkene film in the present embodiment one.
It is to be noted, in another embodiment, by adjusting the reflection parameter when strengthening hydrogen to the corrasion of Graphene, in other words, reduce the carbon source flow, increase hydrogen flowing quantity, reach the suitable shortening time, the Graphene that then adopts preparation method of the present invention to obtain is the single-layer graphene film, and concrete reaction parameter is: argon flow amount is that 200sccm, hydrogen flowing quantity are that 60 ~ 100sccm, carbon source flow are 0.75 ~ 1sccm, temperature of reaction is 910 ℃, and the reaction times is 20 ~ 40min.
As catalytic substrate, the reason that the present invention adopts the germanium material semiconductor base can prepare high-quality Graphene as catalytic substrate is following two aspects compared to the semiconductor base of siliceous composition:
On the one hand, one of prerequisite of preparation Graphene is not form carbide.Carbon solubleness in silicon is far longer than 4% (at), and high molten carbon ability will cause when annealing, and carbon and silicon form a large amount of carbide, have had a strong impact on the catalytic capability of silicon; But, the solubleness of carbon in germanium is very little, when only having fusing point when germanium near boiling temperature, the solubleness of carbon in melting germanium just can reach higher value, and the solubleness near fusing point the time also only is 0.23% (at), so carbon and germanium in the situation of high temperature annealing, can not generate the carbide of germanium, this is consistent with the metallic nickel and the copper that often are used to prepare Graphene.Therefore, as catalytic substrate, select germanium material higher as the quality of the Graphene of catalytic substrate preparation compared to the semiconductor base of siliceous composition.
On the other hand, silicon is oxidized formation natural oxidizing layer in air very easily, and then affects the catalytic capability of silicon base, so when preparing Graphene with silicon as catalytic substrate, in any case the growth regulation parameter is the pattern of uncontrollable Graphene all, also can't obtain high-quality Graphene; But germanium character is more stable, and is not oxidized in air, so when directly preparing Graphene on germanium material, as long as guarantee the vacuum tightness of chamber, affect the catalytic capability on germanium surface just can avoid the oxide compound of germanium to form.
Compared to adopting chemical vapour deposition at conventional base (copper, nickel or quartz, silicon or with the silicon of silica dioxide coating etc.) surface growth Graphene, the present invention adopts chemical gaseous phase depositing process directly to prepare Graphene on semiconductor base, has simplified Graphene preparation technology; Simultaneously by adjusting reaction parameter (concentration ratio of rare gas element, carbonaceous material and hydrogen, temperature of reaction, reaction times), can prepare large size, the controlled Graphene of the number of plies, and there is not the D peak that represents defective in the Raman spectrum of the Graphene of the method preparation, namely eliminate Graphene mass defect, prepared the high-quality Graphene of zero defect; In addition, the present invention is compatible mutually with semi-conductor industry, can promote quickly Graphene in the widespread use in semi-conductor industry circle (fields such as high-performance transparent conductive film, solar cell, touch-screen and high-performance semiconductor device).
Embodiment two
Embodiment two is basic identical with preparation method's technical scheme of embodiment one, difference only is: only the carbon source flow in the step 3) is adjusted in the present embodiment two, be selected from respectively 3sccm, 2sccm, four kinds of situations of 0.75sccm, 0.1sccm, and the Graphene for preparing under these four kinds of differential responses Parameter Conditions compared, all the other something in common see also the associated description of embodiment one.
Identical among the outer remaining reaction parameter of de-carbon source flux and the embodiment one in the present embodiment two, be specially: semiconductor base is germanium, Heating temperature (being temperature of reaction) to the germanium semiconductor substrate is 910 ℃, hydrogen flowing quantity is 50sccm, rare gas element is that argon gas (Ar) and flow are 200sccm, reaction times is 100min, and carbon source is gaseous carbon source methane.
Need to prove, in the present embodiment two, the flow of carbon source methane is selected from respectively 3sccm, 2sccm, 0.75sccm, 0.1sccm four kinds of situations, wherein, when the flow of input methane is 0.1sccm, carbon source is input as the argon gas (Ar) of 2sccm and the mixed gas of methane in the actual process, wherein argon gas (Ar) accounts for 95%, methane accounts for 5%, in other words, argon gas is 1.9sccm in the mixed gas of the argon gas of described 2sccm (Ar) and methane, and methane is 0.1sccm, at this moment, after adding the mixed gas carbon source of this argon gas (Ar) and methane, the actual flow of argon gas is 201.9sccm.
Fig. 3 is the Raman spectrum comparison diagram for the Graphene for preparing under the different carbon source flow conditions in the present embodiment two, as can be seen from Figure 3, in the identical situation of the outer remaining reaction parameter of de-carbon source flux, the carbon amount is lower, it is lower and fade away to represent the D peak of defective in the Graphene that then obtains, when the carbon source methane flow is 0.1sccm, this D peak disappears, show the mass defect of having eliminated Graphene, in addition, for four kinds of different carbon source flow 3sccm, 2sccm, 0.75sccm, 0.1sccm, the relative intensity ratio at G peak and 2D peak shows that all the time in 0.7 ~ 1.3 range the Graphene for preparing under these four kinds of differential responses Parameter Conditions in the present embodiment two all is two-layer.In other words, in the identical situation of the outer remaining reaction parameter of de-carbon source flux, lower carbon amount has obtained high-quality Graphene.
Embodiment three
Embodiment three is basic identical with preparation method's technical scheme of embodiment one, difference only is: in the present embodiment three only the Heating temperature (temperature of reaction) to semiconductor base adjust, be selected from respectively 810 ℃, 850 ℃, 900 ℃ and 910 ℃ of four kinds of situations, and the Graphene for preparing under these four kinds of differential responses Parameter Conditions compared, all the other something in common see also the associated description of embodiment one.
In the present embodiment three except to identical among the remaining reaction parameter the Heating temperature (temperature of reaction) of semiconductor base and the embodiment one, be specially: semiconductor base is germanium, hydrogen flowing quantity is 50sccm, rare gas element is that argon gas (Ar) and flow are 200sccm, reaction times is 100min, carbon source is gaseous carbon source methane, and the flow of methane is 0.1sccm.Need to prove, because device-restrictive, when the flow of input methane when being 0.1sccm, the argon gas that is input as 2sccm (Ar) of carbon source and the mixed gas of methane in the actual process, wherein argon gas (Ar) accounts for 95%, methane accounts for 5%, in other words, argon gas is 1.9sccm in the mixed gas of the argon gas of described 2sccm (Ar) and methane, and methane is 0.1sccm, at this moment, after adding the mixed gas carbon source of this argon gas (Ar) and methane, the actual flow of argon gas is 201.9sccm.
In present embodiment three, the Heating temperature (being temperature of reaction) of germanium semiconductor substrate is selected from respectively 810 ℃, 850 ℃, 900 ℃ and 910 ℃ of four kinds of situations.
Fig. 4 is Raman (Raman) the spectrum comparison diagram for the Graphene for preparing under different heating temperature in the present embodiment three (the being temperature of reaction) condition, as can be seen from Figure 4, except in the identical situation of the remaining reaction parameter the Heating temperature (being temperature of reaction) of germanium semiconductor substrate, Heating temperature (being temperature of reaction) D peak and G peak links together when being 810 ℃, illustrate and comprised some agraphitic carbons, along with the gradually rising of temperature (for 850 ℃, 900 ℃ and 910 ℃ of several situations), D and G peak separate gradually, D fades away at the peak simultaneously, the crystallinity of Graphene is improved, preferably, in Heating temperature (being temperature of reaction) when being 910 ℃, this D peak disappears, show the mass defect of having eliminated Graphene, in addition, for 810 ℃ of four kinds of different Heating temperatures to semiconductor base (temperature of reaction), 850 ℃, 900 ℃ and 910 ℃, the relative intensity ratio at G peak and 2D peak shows that all the time in 0.7 ~ 1.3 range the Graphene for preparing under these four kinds of differential responses Parameter Conditions in the present embodiment three all is two-layer.In other words, except in the identical situation of the remaining reaction parameter the Heating temperature (being temperature of reaction) of germanium semiconductor substrate, high temperature helps to obtain high-quality Graphene.
Embodiment four
Embodiment four is basic identical with preparation method's technical scheme of embodiment one, difference only is: only the reaction times in the step 3) is adjusted in the present embodiment four, be selected from respectively 40min, 60min, four kinds of situations of 80min, 100min, and the Graphene for preparing under these four kinds of differential responses Parameter Conditions compared, all the other something in common see also the associated description of embodiment one.
Identical among remaining reaction parameter in the present embodiment four except the reaction times and the embodiment one, be specially: semiconductor base is germanium, Heating temperature (being temperature of reaction) to the germanium semiconductor substrate is 910 ℃, hydrogen flowing quantity is 50sccm, rare gas element is that argon gas (Ar) and flow are 200sccm, carbon source is gaseous carbon source methane, and the flow of methane is 0.1sccm.Need to prove, because device-restrictive, when the flow of input methane when being 0.1sccm, the argon gas that is input as 2sccm (Ar) of carbon source and the mixed gas of methane in the actual process, wherein argon gas (Ar) accounts for 95%, methane accounts for 5%, in other words, argon gas is 1.9sccm in the mixed gas of the argon gas of described 2sccm (Ar) and methane, and methane is 0.1sccm, at this moment, after adding the mixed gas carbon source of this argon gas (Ar) and methane, the actual flow of argon gas is 201.9sccm.
In present embodiment four, the reaction times in the step 3) is selected from respectively 40min, 60min, four kinds of situations of 80min, 100min.
Fig. 5 is for the Raman of the Graphene for preparing under the differential responses time conditions in the present embodiment four (Raman) spectrum comparison diagram, as can be seen from Figure 5, in the identical situation of remaining reaction parameter except the reaction times, owing to selected low-carbon (LC) amount (methane is 0.1sccm) to react as carbon source, so Graphene poor growth (speed that namely prepares Graphene is slow), gradually prolongation along with the reaction times, the gradually growth of Graphene, thereby reduced the side effect of Graphene, so the D peak descends gradually, preferably, when the reaction times is 100mins, this D peak disappears, show the mass defect of having eliminated Graphene, in addition, for four kinds of different reaction times 40min, 60min, 80min and 100min, the relative intensity ratio at G peak and 2D peak shows that all the time in 0.7 ~ 1.3 range the Graphene for preparing under these four kinds of differential responses Parameter Conditions in the present embodiment four all is two-layer.In other words, in the identical situation of the remaining reaction parameter except the reaction times, the reaction times is more long more to help to prepare high-quality Graphene.
In sum, the preparation method of a kind of Graphene of the present invention, compared to adopting chemical vapour deposition at conventional base (copper, nickel or quartz, silicon or with the silicon of silica dioxide coating etc.) surface growth Graphene, the present invention adopts chemical gaseous phase depositing process directly to prepare Graphene on semiconductor base, has simplified Graphene preparation technology; Simultaneously by adjusting reaction parameter (concentration ratio of rare gas element, carbonaceous material and hydrogen, temperature of reaction, reaction times), can prepare large size, the controlled Graphene of the number of plies, and there is not the D peak that represents defective in the Raman spectrum of the Graphene of the method preparation, namely eliminate Graphene mass defect, prepared the high-quality Graphene of zero defect; In addition, the present invention is compatible mutually with semi-conductor industry, can promote quickly Graphene in the widespread use in semi-conductor industry circle (fields such as high-performance transparent conductive film, solar cell, touch-screen and high-performance semiconductor device).So the present invention has effectively overcome various shortcoming of the prior art and the tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not is used for restriction the present invention.Any person skilled in the art scholar all can be under spirit of the present invention and category, and above-described embodiment is modified or changed.Therefore, have in the technical field under such as and know that usually the knowledgeable modifies or changes not breaking away from all equivalences of finishing under disclosed spirit and the technological thought, must be contained by claim of the present invention.
Claims (7)
1. the preparation method of a Graphene is characterized in that, described preparation method comprises at least:
1) provides the semiconductor substrate;
2) under hydrogen and inert atmosphere, described semiconductor base is heated to 810 ~ 910 ℃;
3) keep step 2) in temperature-resistant, under hydrogen and inert atmosphere to step 2) reaction system in pass into carbon source, adopt the method for chemical vapour deposition in described step 2) the semiconductor-based basal surface that is disposed reacts;
4) reaction is closed described carbon source after complete, and is cooled to room temperature under hydrogen and inert atmosphere, finishes at described semiconductor-based basal surface to prepare Graphene.
2. the preparation method of a kind of Graphene according to claim 1, it is characterized in that: described semiconductor base comprises germanium or gallium arsenide.
3. the preparation method of a kind of Graphene according to claim 1, it is characterized in that: described carbon source is selected from least a of gaseous carbon source, liquid carbon source and solid-state carbon source.
4. the preparation method of a kind of Graphene according to claim 3, it is characterized in that: described gaseous carbon source is methane, acetylene or ethene, described liquid carbon source is methyl alcohol or ethanol, and described solid-state carbon source is polymethylmethacrylate, polystyrene, polydimethylsiloxane.
5. the preparation method of the described a kind of Graphene of any one in 4 according to claim 1, it is characterized in that: in the described step 3), the flow of described carbon source is 0.1 ~ 20sccm; The flow of described hydrogen is 2 ~ 100sccm; The described reaction times is 20 ~ 120min.
6. the preparation method of a kind of Graphene according to claim 1 is characterized in that: described step 1) also comprises the described semiconductor base step that cleans up of water, deionized water, ethanol and acetone respectively.
7. the preparation method of a kind of Graphene according to claim 1, it is characterized in that: the Graphene for preparing in the described step 4) is individual layer or double-layer graphite alkene film.
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